Photographic silver halide emulsions containing polyamine sensitizing agents



3,369,905 PHGTOGRAPHIC SILVER HALIDE EMUL- SIONS CONTAINING POLYAMINESEN- SITIZING AGENTS Jean E. Jones and Charles V. Wilson, Rochester,N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporationof New Jersey No Drawing. Filed Mar. 19, 1963, Ser. No. 266,192 11Claims. (Cl. 96-107) This invention relates to photography andparticularly to sensitizers for photosensitive colloid-silver halideemulsion layers.

Polyalkyleneimino compounds (polyamines) having primary amino end groupsare described for use as chemical sensitizers for photographic silverhalide emulsions in US. Patents No. 2,743,182, patented Apr. 24, 1956,and No. 2,518,698, patented Aug. 15, 1950. Many of these a chemicalsensitizers increase speed of photographic emulsions but have thedisadvantage of substantially increasing fog in the emulsions,especially in emulsions sensitized with sulfur and gold.

An object of the present invention is to provide novel photographiccolloid-silver halide emulsions containing a polyamine sensitizing agentwhich will increase the speed of the emulsion with only very slight orno increase in fog, even in emulsions sensitized with sulfur and gold.

This and other objects of the invention are obtained by incorporatinginto a photographic colloid-silver halide emulsion a polyalkyleneiminocompound having at least one secondary or tertiary amino end group. Evenbetter results are obtained when all of the nitrogen atoms in thepolyamine chain are fully substituted. Effective amounts of sensitizerin the emulsion are usually in the range from 0.03 to 5.0 gramssensitizer per mole silver.

Polyalkyleneimino compounds that are useful as sensitizers according tothe present invention have the formula:

wherein each of R and R represents a member selected from the groupconsistihg of hydrogen, alkyl containing 1-4 carbon atoms, hydroxyalkyl,aryl, aralkyl, alkyl substituted aryl and alkoxy substituted aryl; Rrepresents a member selected from the group consisting of alkylcontaining 1-4 carbon atoms, hydroxyalkyl, aryl, aralkyl, alkylsubstituted aryl and alkoxy substituted aryl; each R is an alkylenechain having from 2-3 carbon atoms in the chain with each of said carbonatoms having attached thereto members selected from the group consistingof hydrogen, alkyl containing 1-4 carbon atoms, aryl of 6- carbon atomsand aralkyl, the alkyl group in each said aralkyl being of 1-2 carbonatoms; n is a positive whole integer from 1-3 and the radical I ls] is aunit in the linear chain of the polyamine.

Specific examples of compounds having the above formula are:

( 1 N,N'-di-beta-hydroxyethylethylenediamine (2)8-amino-3,6-diazaoctanol (3) 3,6,9-triaza-1,1l-undecanediol (4)3,6,9-trimethyltriaza-1,1l-undecanediol (5)4,15-diazaoctadecane-1,18-bisdimethylamine Compounds 1 and 3 in theabove list may be represented by the formula:

wherein R and R are members selected from the group consisting of alkylcontaining 1-4 carbon atoms, hydroxy United States Patent 0 "ice alkyl,aryl, aralkyl, alkyl substituted aryl and alkoxy substituted aryl, R isan alkylene chain having from 2-3 carbon atoms in the chain with each ofsaid carbon atoms having attached thereto members selected from thegroup consisting of hydrogen, alkyl containing 14 carbon atoms, aryl of610 atoms and aralkyl, the alkyl group in said aralkyl being of 1-2carbon atoms, and n is a positive whole integer from 1-3 and the radicalNHR is a unit in the linear chain of the polyamine.

Additional specific examples of compounds having the last formula aboveare:

(6) N,N"'-dimethyltriethylenetetramine (7)N,N"-dimethyldiethylenetriamine (8) N,N'-dimethylethylenediamine (9)N,N'-dibenzylethylenediamine (10) N,N'-di-n-butylethylenediamine l1N,N'-dimethyltrimethylenediamine 12) N,N-dimethyl-1,2-propanediamine (l3N,N'-diphenylethylenediamine The invention may be better understood byreference to the following examples which describe in detail somepreferred embodiments of the invention.

Example I Conventional fast silver bromoiodide-gelatin emulsions,chemically sensitized with sulfur and gold compounds and spectrallysensitized with cyanine dyes were prepared by conventional proceduresand each of the compounds numbered 1-5 above was added respectively to aseparate sample of emulsion in the concentrations shown in Table 1.Control samples of each emulsion were also kept. The sensitized andcontrol emulsion samples were coated by conventional melt coatingprocedures on cellulose acetate film, then chill-set and dried.Respective samples of the film were exposed on an Eastman sensitometerType IB to light of daylight quality for 1. second and were developedfor 5 minutes in Kodak Developer DK-50 at 68 F., then fixed and dried.Relative speed was determined at the exposure necessary to producedensity of 0.2 above fog. Results of the tests in terms of relativespeed, gamma and fog are tabulated in Table 1.

Emulsion number as above) and Con- Relative Gam- Fog centration in GramsPer Speed ma Density Mole Silver Data in Table 1 show results obtainedusing different sensitizers of the class described at concentrationsfrom 0.03 to 3.0 grams per mole silver in the emulsion. Optimum resultswere obtained at concentrations in the magnitude of 0.3 gram per mole,however, the sensitizing effect was appreciable at other concentrations.

Variations from the colloid-silver halide emulsion compositionsdescribed in the examples herein may be made within the scope of thepresent invention. The class of sensitizers defined above are effectiveto increase speed in a wide variety of photosensitive silver halideemulsions familiar to those skilled in the art. The invention includesphotographic emulsions made from suitable colloids other than gelatinand containing other functional addenda as will be familiar to emulsionmakers.

The invention has been described with reference to cer- Q a tainpreferred embodiments but it will be understood that variations andmodifications of the invention as described can be made within the scopeof the invention as defined in the following claims.

We claim: 1 1. A colloid-silver halide photographic emulsion containingat least one linear polyamine sensitizing agent having the formula:

U n Rt N-Ra "NR2 wherein each of R and R represents a member selectedfrom the group consisting of hydrogen, alkyl containing 14 carbon atoms,hydroxyalkyl, aryl, aralkyl, alkyl substituted aryl and alkoxysubstituted aryl; R represents a member selected from the groupconsisting of alkyl containing 1-4 carbon atoms, hydroxyalkyl, aryl,aralkyl, alkyl substituted aryl and alkoxy substituted aryl; each R isan alkylene chain having from 23 carbon atoms in the chain with each ofsaid carbon atoms having attached thereto members selected from thegroup consisting of hydrogen, alkyl containing 1-4 carbon atoms, aryl of6- 10 carbon atoms and aralkyl, the alkyl group in each said aralkylbeing of 1-2 carbon atoms; n is a positive whole integer from 13 and theradical is a unit in the linear chain of the polyamine.

2. A colloidsilver halide photographic emulsion containing at least onelinear polyamine sensitizing agent having the general formula:

wherein R and R are selected from the group consisting of alkyl of 1 to4 carbon atoms, aryl, aralkyl, hydroxy substituted alkyl and'alkylsubstituted aryl and alkoxy substituted aryl; R is an alkylene chainhaving from 2 to 3 carbon atoms in the chain with each of said carbonatoms having attached thereto members selected from the group consistingof hydrogen, alkyl of 1 to 4 carbon atoms, aryl of 6 to 10 carbon atomsand aralkyl, the alkyl group in said aralkyl being of 1 to 2 carbonatoms; and n is a positive whole number from 1 to 3 and the radical, NHRis a unit in the linear chain of the polyamine.

3. An emulsion as set forth in claim 2 wherein said \colloid is gelatin.

4. A colloid-silver halide photographic emulsion containing a linearamine sensitizing agent having the formula:

wherein R is selected from the group consisting of an alkyl radical of 1to 4 carbon atoms and hydroxy substituted alkyl and R is an alkylenechain having 2 to 3 carbon atoms in the chain with each of said carbonatoms having attached thereto members selected from the group consistingof hydrogen and an alkyl of 1 to 4 carbon atoms.

5. A colloid-silver halide photographic emulsion containing at least onelinear polyamine sensitizing agent having the formula:

wherein R and R are hydroxy substituted alkyl, R is an alkylene chainhaving 2 carbon atoms, n is a positive whole integer from 1 to 2, andthe radical NHR is a unit of the linear chain of the polyamine.

6. An emulsion as defined in claim 5 wherein said colloid is gelatin.

7. An emulsion as defined in claim 2 wherein said sensitizing agent isN,N-di-beta-hydroxyethylethylenediamine.

8. An emulsion as defined in claim 1 wherein said sensitizing agent is8-amino-3,6-diazaoctanol.

9. An emulsion as defined in claim 2 wherein said sensitizing agent is3,6,9-triaza-1,11-undecanediol.

10. An emulsion as defined in claim 1 wherein said sensitizing agent is3,6,9-trimethyltriaza-1,1l-undecanediol.

11. A colloid-silver halide photographic emulsion containing4,15-diazaoctadecane 1,18 bisdimethylamine as a linear polyaminesensitizing agent.

References Cited UNITED STATES PATENTS 3,026,203 3/1962 Chamber et al.96-107 2,016,471 10/1935 Wilmanns et al 96-107 2,518,698 8/1950 Lowe etal. 96107 NORMAN G. TORCHIN, Primary Examiner.

J. T. BROWN, Assistant Examiner.

1. A COLLOID-SILVER HALIDE PHOTOGRAPHIC EMULSION CONTAINING AT LEAST ONELINEAR POLYAMINE SENSITIZING AGENT HAVING THE FORMULA: